JPS6316554A - Non-sintered type cadmium anode for alkaline storage battery - Google Patents
Non-sintered type cadmium anode for alkaline storage batteryInfo
- Publication number
- JPS6316554A JPS6316554A JP61159478A JP15947886A JPS6316554A JP S6316554 A JPS6316554 A JP S6316554A JP 61159478 A JP61159478 A JP 61159478A JP 15947886 A JP15947886 A JP 15947886A JP S6316554 A JPS6316554 A JP S6316554A
- Authority
- JP
- Japan
- Prior art keywords
- cadmium
- indium
- anode
- cathode
- active material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 37
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052738 indium Inorganic materials 0.000 claims abstract description 18
- 239000011149 active material Substances 0.000 claims abstract description 17
- 150000002472 indium compounds Chemical class 0.000 claims abstract description 13
- PLLZRTNVEXYBNA-UHFFFAOYSA-L cadmium hydroxide Chemical compound [OH-].[OH-].[Cd+2] PLLZRTNVEXYBNA-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims description 5
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 claims description 5
- 229910003437 indium oxide Inorganic materials 0.000 claims description 2
- IGUXCTSQIGAGSV-UHFFFAOYSA-K indium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[In+3] IGUXCTSQIGAGSV-UHFFFAOYSA-K 0.000 claims description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 2
- LKEDUJPRSZGTHZ-UHFFFAOYSA-H indium(3+);oxalate Chemical compound [In+3].[In+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O LKEDUJPRSZGTHZ-UHFFFAOYSA-H 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 2
- 238000003487 electrochemical reaction Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000008151 electrolyte solution Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- -1 ferric oxide Chemical compound 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002471 indium Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/246—Cadmium electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/44—Alloys based on cadmium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】 Ｈ）産業上の利用分野 この発明はカドミウム陰極に関し、詳しくは。[Detailed description of the invention] H) Industrial application field This invention relates to cadmium cathodes, and more particularly.
ニッケルーカドミウム蓄電池の如きアルカリ蓄電池・等
の陰極として用いられ、生活物質としての酸化カドミウ
ムまたは水酸化カドミウム粉末と、予備充電生成物とし
ての金属カドミウム粉末とを含有した混練物を導電芯体
に塗布して作成されるカドミウム陰極の改良に関するも
のである。Used as a cathode in alkaline storage batteries such as nickel-cadmium storage batteries, etc., and coats a conductive core with a kneaded material containing cadmium oxide or cadmium hydroxide powder as a living substance and metal cadmium powder as a pre-charging product. This paper relates to the improvement of cadmium cathodes made by
（ロ）従来の技術
ニッケルーカドミウム蓄電池等に用いられるカドミウム
陰極としては、製造工程が簡易で製造コストの安いペー
スト式の如き非焼結式のカドミウム陰極が工業的に広く
用いられている。この種のカドミウム陰極は、酸化カド
ミウム粉末や水酸化カドミウム粉末等の活物質を糊料液
と共ζ（混練して形成したペーストを導電芯体に塗着し
充填し、次いで乾燥及び化成処理を施した後、水洗及び
乾燥を行なう等して製造されるが、活物質と導電芯体と
の結着力が弱いので、化成工程などにおける活物質の剥
がれや脱落が著しく、それ故、充放電サイクルにおける
容量劣化が大きい等という欠点がある。(b) Prior Art As cadmium cathodes used in nickel-cadmium storage batteries, etc., non-sintered cadmium cathodes such as paste-type cadmium cathodes, which have a simple manufacturing process and are low in manufacturing cost, are widely used industrially. This type of cadmium cathode is made by kneading an active material such as cadmium oxide powder or cadmium hydroxide powder with a paste solution, applying the paste to the conductive core and filling it, then drying and chemical conversion treatment. After application, it is manufactured by washing with water and drying, but since the binding force between the active material and the conductive core is weak, the active material peels off or falls off during the chemical conversion process, etc., and therefore the charge/discharge cycle is shortened. There are drawbacks such as large capacity deterioration.
このため１例えば特公昭５８−３２７４４号公報に開示
されているように、上記ペースト中に含有させる活物質
として主活物質としての酸化カドミウム粉末等と予備充
電生成物としての金属カドミウム粉末との混合物を用い
ることで、ペースト式カドミウム陰極における化成工程
を実質上不要とし、もって充放電サイクルの進行に伴う
電池容量劣化を防止することが提案されている。For this purpose, 1, for example, as disclosed in Japanese Patent Publication No. 58-32744, a mixture of cadmium oxide powder as a main active material and metal cadmium powder as a pre-charge product is used as the active material to be contained in the paste. It has been proposed that by using a paste-type cadmium cathode, the chemical formation step in the paste-type cadmium cathode is substantially unnecessary, thereby preventing battery capacity deterioration as the charge/discharge cycle progresses.
（ハ）発明が解決しようとする問題点
しかしながら、このような目的で用いる金属カドミウム
粉末として、上記特公昭５８−３２７４４号公報に開示
されているカドミウム塩溶液中に亜鉛粉末とニッケル粉
末との混合粉末を分散し、カドミウムと亜鉛とのイオン
化傾向の差を利用した置換反応によシ析出させて生成し
たニッケルを含む海綿状金属カドミウムを粉砕処理する
という方法 で得たもの
を用いた場合、得られ念金属カドミウム粉末は利用率が
低く、電極自体の利用率も低くなる。(c) Problems to be Solved by the Invention However, as a metal cadmium powder used for such a purpose, a mixture of zinc powder and nickel powder in a cadmium salt solution disclosed in the above-mentioned Japanese Patent Publication No. 58-32744. When using a method of dispersing powder and pulverizing spongy metallic cadmium containing nickel, which is precipitated by a substitution reaction that takes advantage of the difference in ionization tendency between cadmium and zinc, The utilization rate of the metal cadmium powder is low, and the utilization rate of the electrode itself is also low.
また一方、カドミウム極の利用率を向上させるために特
開昭５１−１５０６４６号公報には、酸化第２鉄等の鉄
を添加することが提案されているが、充放電サイクルの
進行に伴ない溶出した鉄イオンが電極に移行して陽極容
蓋の低下を招き、更には自己放電が大きいという問題点
がある。On the other hand, in order to improve the utilization rate of the cadmium electrode, Japanese Patent Application Laid-Open No. 150646/1983 proposes adding iron such as ferric oxide, but as the charge/discharge cycle progresses, There are problems in that eluted iron ions migrate to the electrode, causing deterioration of the anode container, and furthermore, self-discharge is large.
に）問題点を解決するための手段
本発明は、アルカリ蓄電池用非焼結式カドミウム陰極に
インジウム或いはインジウム化合物を添加することを特
徴とするものであシ、前記インジウム或いはインジウム
化合物の添加量としてはインジウム換算で活物質カドミ
ウムに対して０．０１〜５．００重量％であることが好
ましい。尚、インジウム化合物は酸化物、水酸化物もし
くは塩の形態として添加することが可能である。B) Means for solving the problem The present invention is characterized in that indium or an indium compound is added to a non-sintered cadmium cathode for an alkaline storage battery, and the amount of the indium or indium compound added is is preferably 0.01 to 5.00% by weight based on the active material cadmium in terms of indium. Note that the indium compound can be added in the form of an oxide, hydroxide, or salt.
（ホ）作 用
インジウム或はインジウム化合物を含んだカドミウム陰
極をアルカリ電解液中で充放電を行なうと、充電時カド
ミウム金属結晶中にインジウム原子が置換され、カドミ
ウム金属結晶の格子欠陥生じ結晶状態が不安定化する。(e) Effect When a cadmium cathode containing indium or an indium compound is charged and discharged in an alkaline electrolyte, indium atoms are substituted in the cadmium metal crystal during charging, causing lattice defects in the cadmium metal crystal and changing the crystal state. destabilize.
これはインジウムの原子番号が４９、カドミウムの原子
番号が４８であり、原子量がきわめて近い値であること
に基づく。尚この構造は電子の状態に影響が大きいため
、電気化学的な反応が活性化し、利用率の高い金属カド
ミウムが生成し、カドミウム陰極自体の利用率が向上す
る。This is based on the fact that the atomic number of indium is 49 and the atomic number of cadmium is 48, and their atomic weights are extremely close to each other. Since this structure has a large effect on the state of electrons, electrochemical reactions are activated, metal cadmium with a high utilization rate is produced, and the utilization rate of the cadmium cathode itself is improved.
（へ）実 施 例
カドミウム活物質として酸化カドミウム８０重量部と金
属カドミウム２０重量部と、金属インジウム粉末をカド
ミウム活物質に対して０．５重量％添加し、水６８重量
部、水溶性糊料としてメチルセルロース１．５重量部、
および補強材としてアクリル短繊維１．８重量部の割合
で混合し、活物質ペーストを得る。この活物質ペースト
をパンチングメタル集電体に塗着、乾燥し所定の寸法に
切断し本発明カドミウム陰極を得た。この陰極をニッケ
ル板を対極とし、電解液濃度２５９６の水酸化カリウム
溶液中で充放電を行ない陰極の利用率を計算し友。この
時、充電は０．１５Ｃの電流で１５時間行ない、放電は
０．６Ｃの電流で放電終止電圧−１ＯＶ （ＶＳ、Ｈｇ
／Ｈｇ０）とした。(F) Example 80 parts by weight of cadmium oxide and 20 parts by weight of metallic cadmium as a cadmium active material, 0.5% by weight of metallic indium powder relative to the cadmium active material, 68 parts by weight of water, and a water-soluble glue. as 1.5 parts by weight of methylcellulose,
and 1.8 parts by weight of short acrylic fibers as a reinforcing material are mixed to obtain an active material paste. This active material paste was applied to a punched metal current collector, dried, and cut into predetermined dimensions to obtain a cadmium cathode of the present invention. Using a nickel plate as the counter electrode, this cathode was charged and discharged in a potassium hydroxide solution with an electrolyte concentration of 2596, and the utilization rate of the cathode was calculated. At this time, charging was carried out for 15 hours at a current of 0.15C, and discharging was carried out at a current of 0.6C at the end of discharge voltage -1OV (VS, Hg
/Hg0).
図はカドミウム活物質に対するインジウムの含有量と陰
極の利用率の関係を示したものであり。The figure shows the relationship between the content of indium in the cadmium active material and the utilization rate of the cathode.
陰極利用率の算出は次のようにして行った。Calculation of the cathode utilization rate was performed as follows.
図に示されるようにカドミウム活物質中にインジウムが
添加されていると、陰極利用率が向上することが伺える
。インジウム或いはインジウム化合物の添加量としては
、インジウム換算でカドミウム活物質に対して０．０１
〜５．００重量％が好ましく特に０．０１〜２．００重
量％の範囲に２いて最大の利用率が得られる。As shown in the figure, it can be seen that when indium is added to the cadmium active material, the cathode utilization rate is improved. The amount of indium or indium compound added is 0.01 in terms of indium relative to the cadmium active material.
It is preferably in the range of 0.01 to 2.00% by weight, particularly 0.01 to 2.00% by weight, to obtain the maximum utilization rate.
尚、実施例においては添加剤として金属インジウムを用
いたが、その他にインジウム化合物として酸化インジウ
ム、水酸化インジウム、ｉ ｆｃインジウムの塩として
添加することもできる。In the examples, metallic indium was used as the additive, but other indium compounds such as indium oxide, indium hydroxide, and ifc indium salts may also be added.
（ト）発明の効果
この発明のカドミウム陰極によれば利用率の高いカドミ
ウム陰極が得られ、陰極容量の向上が図れ、陰極の容量
増加分だけ陽極の容量を高く設定できるので電池容量が
増加する。また陽極容量を従来通りに設定した場合は陰
極の利用率が高く陰極支配になシにくいので、過充電特
性を向上せしめることができる。(G) Effects of the Invention According to the cadmium cathode of the present invention, a cadmium cathode with a high utilization rate can be obtained, the cathode capacity can be improved, and the capacity of the anode can be set higher by the increase in the capacity of the cathode, so the battery capacity can be increased. . Furthermore, when the anode capacity is set as before, the utilization rate of the cathode is high and cathode domination is less likely to occur, so that overcharging characteristics can be improved.
図はカドミウム活物質に対するインジクム含有量と陰項
利用率の関係を示したものである。The figure shows the relationship between the indicium content and the negative term utilization rate for cadmium active materials.
Claims (3)
ミウムと、予備充電生成物質としての金属カドミウムと
、インジウム或いはインジウム化合物とよりなることを
特徴とするアルカリ蓄電池用非焼結式カドミウム陰極。(1) A non-sintered cadmium cathode for an alkaline storage battery characterized by comprising cadmium oxide or cadmium hydroxide as a main active material, metal cadmium as a pre-charge product, and indium or an indium compound.
は、前記カドミウム活物質に対してインジウム換算で０
．０１〜５．００重量％であることを特徴とする特許請
求の範囲第（１）項記載のアルカリ蓄電池用非焼結式カ
ドミウム陰極。(2) The amount of the indium or indium compound added is 0 in terms of indium relative to the cadmium active material.
．． 01 to 5.00% by weight of the non-sintered cadmium cathode for an alkaline storage battery according to claim (1).
インジウム、シュウ酸インジウムから選ばれたものであ
ることを特徴とする特許請求の範囲第（１）項記載のア
ルカリ蓄電池用非焼結式カドミウム陰極。(3) The non-sintered cadmium cathode for an alkaline storage battery according to claim (1), wherein the indium compound is selected from indium hydroxide, indium oxide, and indium oxalate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61159478A JPH0724216B2 (en) | 1986-07-07 | 1986-07-07 | Non-sintered cadmium cathode for alkaline storage batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61159478A JPH0724216B2 (en) | 1986-07-07 | 1986-07-07 | Non-sintered cadmium cathode for alkaline storage batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6316554A true JPS6316554A (en) | 1988-01-23 |
| JPH0724216B2 JPH0724216B2 (en) | 1995-03-15 |
Family
ID=15694648
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61159478A Expired - Lifetime JPH0724216B2 (en) | 1986-07-07 | 1986-07-07 | Non-sintered cadmium cathode for alkaline storage batteries |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0724216B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007109501A (en) * | 2005-10-13 | 2007-04-26 | Furukawa Battery Co Ltd:The | Alkaline storage battery |
| JP2013077406A (en) * | 2011-09-30 | 2013-04-25 | Sanyo Electric Co Ltd | Alkali storage battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61193363A (en) * | 1985-02-20 | 1986-08-27 | Shin Kobe Electric Mach Co Ltd | Nickel-cadmium alkaline storage battery |
-
1986
- 1986-07-07 JP JP61159478A patent/JPH0724216B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61193363A (en) * | 1985-02-20 | 1986-08-27 | Shin Kobe Electric Mach Co Ltd | Nickel-cadmium alkaline storage battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007109501A (en) * | 2005-10-13 | 2007-04-26 | Furukawa Battery Co Ltd:The | Alkaline storage battery |
| JP2013077406A (en) * | 2011-09-30 | 2013-04-25 | Sanyo Electric Co Ltd | Alkali storage battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0724216B2 (en) | 1995-03-15 |
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